CN102471590A

CN102471590A - Low-permittivity resin composition

Info

Publication number: CN102471590A
Application number: CN2010800319093A
Authority: CN
Inventors: 矢野聪宏; 小松正树
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2009-07-14
Filing date: 2010-07-06
Publication date: 2012-05-23
Anticipated expiration: 2030-07-06
Also published as: US8785522B2; US20120123021A1; EP2455428B1; CN102471590B; WO2011007698A1; EP2455428A1; EP2455428A4

Abstract

Provided is (1) a low-permittivity resin composition, having a sufficiently low permittivity and dielectric loss tangent, wherein hollow silica particles are dispersed in a matrix resin, said hollow silica particles having a mean diameter between 0.05 [mu]m and 3 [mu]m and a BET specific surface area of less than 30 m2/g. Also provided is (2) a low-permittivity film comprising said low-permittivity resin composition. Further provided is (3) a method for manufacturing the low-permittivity resin composition and low-permittivity film, said method including a step which: prepares either hollow silica particles (A) that contain air inside or core-shell silica particles (B) that enclose a material that is eliminated upon firing, thereby forming hollow regions; fires same at a temperature exceeding 950 DEG C, thereby preparing hollow silica particles (C); and prepares a liquid dispersion wherein the hollow silica particles are dispersed in a matrix resin forming material. Additionally provided is a coating agent (4) for a low-permittivity film, wherein the aforementioned hollow silica particles are dispersed in a matrix resin forming material.

Description

Low dielectric resin composition

Technical field

The method of manufacture and the low dielectric film that the present invention relates to low dielectric resin composition, low dielectric film, low dielectric resin composition and low dielectric film are used the coating agent.

Background technology

The e-machines such as LSI that on CPU or storer, use; Though high in recent years mechanization is more and more progressive; Operating frequency rises; The miniaturized etc. of device is improving, but the transmission loss that produces along with the increase of operating frequency on the other hand increases, and the problems such as increase that the distribution miniaturization produces the dead time are also enlarging.

In order to address these problems, require to develop the low-k that in the multi-layer wiring structure of circuit, uses, the insulating material of low-dielectric loss angle tangent.In order to reduce the specific inductivity of interlayer dielectric, carried out in the inner investigation that imports the space of film, if but import big or small uneven space in order to reduce specific inductivity, then can produce the problem that film toughness reduces.

In patent documentation 1; The film formation property liquid that is made up of ceramic precursor, catalyzer, tensio-active agent and solvent through modulation is disclosed; And it is removed desolvate, thereby make the method for manufacture that specific inductivity is shown as 2～3 ceramic membranes such as mesoporous silicon dioxde film on substrate.

In patent documentation 2; Film having low dielectric constant is disclosed; This film having low dielectric constant is to contain the film having low dielectric constant that the porous insert of the Si oxide of organic group constitutes; At least a portion Siliciumatom forms carbon-silicon key in this Si oxide on the organic group more than 2 places, and porous insert is the mesoporous porous insert with center pore diameter of 1～30nm.

But, problem that can't be general below patent documentation 1 and 2 exists: need firing process in order to remove the tensio-active agent that when making film, uses, limit the kind of substrate etc.

In addition; In patent documentation 3, the method that forms insulating film with low dielectric constant is disclosed, said method be with the solution coat that contains particulate, resin and solvent on substrate to form after the film; Heat this substrate; Thereby the formation insulating film with low dielectric constant, wherein said particulate contains the key of Siliciumatom and Sauerstoffatom, and has emptying aperture.

In patent documentation 4, disclose low dielectric resin composition, and low dielectric resin composition contained be dipped in the base material, heat drying and the mylar that forms.Wherein, In the low dielectric resin composition that contains hollow particle and thermosetting resin, using mean porosities is that 30～80 volume % and median size are that the silica dioxide granule of 0.1～20 μ m is processed the low dielectric resin composition that specific inductivity, tangent of the dielectric loss angle are reduced as hollow particle.

But, can't meet the demands aspect patent documentation 3 or 4 specific inductivity, the tangent of the dielectric loss angle at film.

The prior art document

Patent documentation

Patent documentation 1: the spy opens the 2001-226171 communique

Patent documentation 2: the spy opens the 2003-86676 communique

Patent documentation 3: the spy opens the 2005-167266 communique

Patent documentation 4: the spy opens the 2008-031409 communique

Summary of the invention

The present invention relates to following (1)～(6).

(1) low dielectric resin composition, in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m by the hollow silica particles dispersed for it ²/ g.

(2) low dielectric resin composition; Its by the hollow silica particles dispersed in matrix resin and form; Said hollow silica particulate median size is 0.05～1 μ m; All have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.

(3) low dielectric resin composition, in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m by the hollow silica particles dispersed for it, porosity (porosity) is 30～90%, and the BET specific surface area is less than 30m ²/ g.

(4) low dielectric film, its low dielectric resin composition by said (1)～(3) forms.

(5) method of manufacture of the low dielectric resin composition of said (1)～(3).

(6) low dielectric film is used the coating agent, and its hollow silica particles dispersed of being put down in writing by said (1)～(3) forms in the material in matrix resin and forms.

Embodiment

The method of manufacture and the low dielectric film of low dielectric film, low dielectric resin composition and the low dielectric film that the present invention relates to a kind of low dielectric resin composition with enough low specific inductivity, tangent of the dielectric loss angle, formed by this dielectric combination are used the coating agent.

Present inventors find that hollow silica particles dispersed through will having ad hoc structure in matrix resin, can solve said problem.

That is, the present invention is specifically related to following [1]～[9].

[1] low dielectric resin composition, in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m by the hollow silica particles dispersed for it ²/ g.

[2] low dielectric resin composition; Its by the hollow silica particles dispersed in matrix resin and form; Said hollow silica particulate median size is 0.05～1 μ m; All have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.

[3] low dielectric resin composition, in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m by the hollow silica particles dispersed for it, porosity is 30～90%, and the BET specific surface area is less than 30m ²/ g.

[4] low dielectric film, its low dielectric resin composition by said (1)～(3) forms.

[5] method of manufacture of the low dielectric resin composition of said [1]～[3], it comprises following operation (I)～(III):

Operation (I): the hollow silica particle (A) of air is contained in particle modulator inside, and perhaps modulation is encapsulated with the operation through the core-shell silica particle (B) that burns till the material that understanding disappears forms the hollow part;

Operation (II): the said hollow silica particle (A) or the said core-shell silica particle (B) that under surpassing 950 ℃ temperature, obtain in operation (I) burn till, with the operation of modulation hollow silica particle (C);

Operation (III): the hollow silica particle (C) that obtains in the operation (II) is scattered in matrix resin forms the operation of modulating dispersion liquid in the material.

[6] method of manufacture of low dielectric film, it comprises said operation (I)～(III) and following operation (IV):

Operation (IV): the dispersion liquid that obtains in the said operation (III) is coated on the substrate, made its solidified operation then.

[7] low dielectric film is used the coating agent, and it is formed in the material in matrix resin by the hollow silica particles dispersed and forms, and said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m ²/ g.

[8] low dielectric film is used the coating agent; It is formed in the material in matrix resin by the hollow silica particles dispersed and forms; Said hollow silica particulate median size is 0.05～1 μ m; All have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.

[9] low dielectric film is used the coating agent, and it is formed in the material in matrix resin by the hollow silica particles dispersed and forms, and said hollow silica particulate median size is 0.05～3 μ m, and porosity is 30～90%, and the BET specific surface area is less than 30m ²/ g.

[low dielectric resin composition and low dielectric film]

The 1st low dielectric resin composition of the present invention is characterized in that, in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m by the hollow silica particles dispersed ²/ g.Low dielectric film of the present invention is characterized in that, is formed by this low dielectric resin composition.

The 2nd low dielectric resin composition of the present invention; It is characterized in that; By the hollow silica particles dispersed in matrix resin and form; Said hollow silica particulate median size is 0.05～1 μ m, all have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.Low dielectric film of the present invention is characterized in that, is formed by this low dielectric resin composition.

The 3rd low dielectric resin composition of the present invention; It is characterized in that in matrix resin and form, said hollow silica particulate median size is 0.05～3 μ m by the hollow silica particles dispersed; Porosity is 30～90%, and the BET specific surface area is less than 30m ²/ g.

In addition, low dielectric film of the present invention is characterized in that, is formed by this low dielectric resin composition.

In low dielectric resin composition of the present invention and low dielectric film,, reduce its specific inductivity, tangent of the dielectric loss angle with hope through disperseing to contain hollow silica particle with said ad hoc structure.Therefore this thinks can not reduce voidage because matrix resin can not be present in hollow silica particulate hollow bulb, and can reduce the molding that formed by this resin combination and specific inductivity, the tangent of the dielectric loss angle of film.

The specific inductivity of low dielectric film for example under the frequency of 1MHz, is preferably below 3.5, further is preferably below 3.2, is more preferably below 3.0, is preferably 1.5～3.0 especially.In addition, the mensuration of specific inductivity can be used LCR tester or electric impedance analyzer etc., carries out through domestic methods such as electrode contact process or electrode noncontact methods.

In addition, the tangent of the dielectric loss angle of low dielectric film for example is preferably below 0.01 under the condition determination of record in an embodiment, further is preferably below 0.0095, is more preferably below 0.009.

The thickness of low dielectric film has no particular limits, but the viewpoint from making and finding the low-k performance is preferably 10～700 μ m, further is preferably 30～500 μ m, is more preferably 50～300 μ m.

[hollow silica particle]

In the present invention, using [1] median size is that 0.05～3 μ m and BET specific surface area are less than 30m ²The hollow silica particle of/g (below, be called " hollow silica particle [1] "), [2] median size be 0.05～1 μ m, all have more than the 80 quality % in the particle median size ± 30% with interior particle diameter and BET specific surface area less than 30m ²The hollow silica particle of/g (below, be called " hollow silica particle [2] "), perhaps [3] median size be 0.05～3 μ m, porosity be 30～90% and the BET specific surface area less than 30m ²The hollow silica particle of/g (below, be called " hollow silica particle [3] ").Below, be generically and collectively referred to as " hollow silica particle [1]～[3] ", be also referred to as " hollow silica particle " perhaps " hollow silica particle (C) " separately.

The median size of hollow silica particle [1] can consider that purposes etc. suitably adjusts, and its number average bead diameter is preferably 0.1～3 μ m, further is preferably 0.15～2.5 μ m, is more preferably 0.2～2.2 μ m.

The median size of hollow silica particle [2] can consider that purposes etc. suitably adjusts, and its number average bead diameter is preferably 0.1～1 μ m, further is preferably 0.15～0.9 μ m, is more preferably 0.2～0.8 μ m.

The median size of hollow silica particle [3] can consider that purposes etc. suitably adjusts, and its number average bead diameter is preferably 0.1～2.7 μ m, further is preferably 0.15～2.5 μ m, is more preferably 0.2～2.2 μ m.

Under situation about using as the resins in film form compsn, hollow silica particulate median size is preferred less, and its number average bead diameter is preferably 0.05～1 μ m, further is preferably 0.1～0.9 μ m, is more preferably 0.2～0.8 μ m.

On the other hand, under the identical situation of porosity, hard intensity is high more more can to expect median size, and in this case, number average bead diameter is preferably 1～3 μ m, further is preferably 1～2.7 μ m, is more preferably 1～2.5 μ m.

Under situation about using as the resins in film form compsn; The hollow silica particle is preferred all more than the particulate 80 quality %; Further more than the preferred 85 quality %; Be more preferably more than the 90 quality %, have median size ± 30% with interior particle diameter more than the preferred especially 95 quality %, hope by particle diameter very the homogeneous granules crowd constitute.

In addition, from viewpoints such as raising dielectric properties, hollow silica particulate porosity can be preferably 30～90%, further is preferably 35～85%, is more preferably 38～80%.

In addition, hollow silica particulate BET specific surface area, the viewpoints such as stable maintenance from encapsulation object are preferably 25m ²Below/the g, further be preferably 20m ²Below/the g, be more preferably 18m ²Below/the g.

The hollow silica particle is preferably locating do not show peak at a distance from (d) less than the suitable diffraction angle of the scope of 1nm (2 θ) with interplanar in powder x-ray diffraction (XRD) is measured.

In addition, the hollow silica particle does not show basically that preferably the above micropore of 1nm distributes in micropore diameter distributes.The mean thickness of housing department preferably can keep with the hollow silica particle as the scope of the intensity of carrier in thin thickness, the mean diameter of hollow bulb (average volume) is from the preferred big diameter of the viewpoint that keeps encapsulation object morely.From these viewpoints, the mean thickness of housing department is generally 0.5～500nm, is preferably 2～400nm, is more preferably 3～300nm.

The ratio of [mean thickness of housing department/hollow silica particulate median size] is generally 0.01～0.9, is preferably 0.05～0.8, is more preferably 0.1～0.7.

The mean thickness of hollow silica particulate median size, housing department can be through suitably adjusting as the creating conditions of the hollow silica particle (A) of raw material, particle diameter that the hollow part forms material, firing condition etc.

[method of manufacture of low dielectric resin composition]

The method of manufacture of low dielectric resin composition of the present invention has no particular limits, as long as according to the method that comprises following operation (I)～(III), just can efficiently make.

Operation (I): particle modulator inside contain air hollow silica particle (A) (below; Be also referred to as " hollow silica particle (A) " separately); Perhaps modulation is encapsulated with the operation of core-shell silica particle (B) through burning till the material form the hollow part of can disappearing (below, be also referred to as " core-shell silica particle (B) ");

Below, to the detailed process of operation (I)～(III) and use therein each become to grade and describe.

Operation (I)

Operation (I) is the operation of modulation hollow silica particle (A) or core-shell silica particle (B).So long as the method for hollow silica particle (A) or core-shell silica particle (B) of can making all has no particular limits, be more preferably the method that comprises following operation A～D.

Operation A: modulation contains the operation of the aqueous solution of following compound: the polymer beads of 0.1～50g/L (a-1), or the hydrophobic organic compound (a-2) of 0.1～100mmol/L; More than one the material of from the represented quaternary ammonium salt in formula (1) and (2), selecting (b) with 0.1～100mmol/L; And the silicon source (c) of passing through hydrolysis meeting generation silanol compound of 0.1～100mmol/L.

[R ¹(CH ₃) ₃N] ⁺X ^- (1)

[R ¹R ²(CH ₃) ₂N] ⁺X ^-?(2)

(in the formula, R ¹And R ²Represent independently that respectively carbonatoms is 4～22 straight chain shape or branched-chain alkyl, X representes univalent anion.)

Process B: under 10～100 ℃ temperature; The aqueous solution that obtains in the agitating procedure (A); The operation of the aqueous dispersions of modulation primary nuclei shell mould silica dioxide granule; Wherein, said primary nuclei shell mould silica dioxide granule has the shell that is made up of silicon-dioxide, and has polymer beads (a-1) or hydrophobic organic compound (a-2) in the nuclear.

Operation C: the operation of isolated nuclei shell mould silica dioxide granule (B) in the aqueous dispersions that from process B, obtains.

Step D: the core-shell silica particle (B) that obtains among the operation C is burnt till, obtain the operation of hollow silica particle (A).

Describe to following operation A～D.

[operation A]

(polymer beads (a-1))

As polymer beads used in operation A (a-1), the particle of preferably from cation property copolymer, nonionic polymkeric substance and amphiphilic polymers, selecting of polymkeric substance more than a kind, preferably water-insoluble polymer in fact.

The median size of used polymer beads in operation A～D; It is hollow silica particulate characteristic of the present invention; In order to realize obtaining the purpose of nominal particle size and the uniform compound of size distribution, be preferably 0.02 μ m～1 μ m, further be preferably 0.05 μ m～0.9 μ m; Be more preferably 0.1 μ m～0.8 μ m, be preferably 0.12 μ m～0.7 μ m especially.In addition; Polymer beads is preferred all more than the particulate 80 quality %; Further be preferably more than the 85 quality %; Be more preferably more than the 90 quality %, be preferably especially more than the 95 quality % and have median size ± 30%, hope especially by the unusual polymer beads that constitutes of homogeneous granules crowd of particle diameter with interior particle diameter.

(cation property copolymer)

As cation property copolymer, preferably in, under the condition that cats product exists, form polymer emulsion and can the dispersive polymkeric substance with the medium of external phase as water system.Preferably under the condition that cats product exists,, particularly contain the monomer mixture of ethylene unsaturated monomer, resulting cation property copolymer with cationic group with known method emulsion polymerization cationic monomer.

As cationic monomer, can lift and have amino monomeric sour corrective, or this monomer carried out the quaternized quaternary ammonium salt that forms etc. with quaternizing agent.

As the object lesson of cationic monomer, further preferably have (methyl) propenoate of dialkyl amido or trialkyl ammonium, most preferably have (methyl) propenoate of dialkyl amido or trialkyl ammonium.

In addition, in this manual, (methyl) propenoate be meant propenoate, methacrylic ester or they both.

Cation property copolymer contains the formation unit that derives from said cationic monomer; But decationize property monomer constitutes beyond the unit, further preferably contain derive from hydrophobic monomer, particularly derive from alkyl (methyl) propenoate, contain the formation unit of hydrophobic monomer such as aromatic nucleus monomer.As its suitable example, can enumerate: alkyl (methyl) propenoate, it has, and carbonatoms is 1～30, preferred carbonatoms is 3～22, further preferred carbonatoms is 3～18 alkyl; Styrene monomer such as vinylbenzene or 2-methyl styrene; (methyl) acrylic acid aryl ester of benzyl (methyl) propenoate etc.; Contain carbonatoms and be the vinyl monomer of 6～22 aromatic series base; Perhaps Vinyl Acetate Monomer etc.Wherein most preferably alkyl (methyl) propenoate, vinylbenzene.

In addition, hydrophobic monomer is meant that solvability for water is low and form the polymerizability organic cpds that is separated with water.It is more than 0, to be preferably more than 0.5 that hydrophobic monomer can be lifted the LogP value, and is the compound below 25.At this, LogP is meant the logarithmic value of partition ratio of the 1-octanol/water of chemical substance, through SRC ' s LOGKOW/KOWWIN Program, and the numerical value that calculates with fragment method (fragment approach).Specifically; Be that STRUCTURE DECOMPOSITION with chemical substance becomes its integrant; The hydrophobicity fragment constant (with reference to Meylan, W.M.and P.H.Howard.1995.Atom/fragment contribution method for estimating octanol-water partition coefficients.J.Pharm.Sci.84:83-92) that accumulative total is tried to achieve each fragment and had.

The cationic monomer that constitutes cation property copolymer constitutes the unit can be on a small quantity, constitute cation property copolymer also basically the origin formation unit that comes from hydrophobic monomer constitute.Cationic monomer formation unit shared in the cation property copolymer is 70～100 quality % with the unitary total amount of formation that derives from hydrophobic monomer, is preferably 80～100 quality %, is preferably 95～100 quality % especially.Particularly from viewpoint from particle formation property; The weight ratio of [(deriving from the formation unit of cationic monomer)/(deriving from the formation unit of hydrophobic monomer)] is preferably 0.001～0.5; Further be preferably 0.002～0.3, be preferably 0.003～0.1 especially.

(nonionic polymkeric substance)

The nonionic polymkeric substance is meant the polymkeric substance that in the aqueous solution, does not have electric charge.The nonionic polymkeric substance is to derive from the monomer with electric charge, and promptly the polymkeric substance of non-ionic monomer can obtain through method polymerization non-ionic monomers such as known emulsion polymerization method, emulsifier-free polymerizations.

As non-ionic monomer, can enumerate the hydrophobic monomer in the explanation of cation property copolymer, lifted ([0015], [0016] section).As its preferred example, can to enumerate from having carbonatoms be 1～30, be preferably carbonatoms is 3～22, further is preferably more than one monomers of selecting alkyl (methyl) propenoate, vinyl acetate between to for plastic and the vinylbenzene of 3～18 alkyl.

As the object lesson of nonionic polymkeric substance, can enumerate PS, ethyl propenoate ethyl methacrylate copolymers, ethyl propenoate methylmethacrylate copolymer, Octyl acrylate styrol copolymer, Bing Xisuandingzhi acetate ethylene copolymer, TEB 3K Bing Xisuandingzhi Octyl acrylate multipolymer, vinyl acetate between to for plastic styrol copolymer, vinyl pyrrolidone styrol copolymer, Bing Xisuandingzhi, PS vinyl resin etc.

In cation property copolymer, nonionic polymkeric substance and amphiphilic polymers, preferred cationic property polymkeric substance and nonionic polymkeric substance, the viewpoint from the easy formation of hollow silica dioxide granule (A) is more preferably cation property copolymer.

On the empty in the mill silica dioxide granule (A), use the polymkeric substance that in fact is not dissolved in water, therefore can adopt the method for the polymerization ratio that improves hydrophobic monomer, crosslinked method etc.

Suitable example as relevant polymkeric substance; Can enumerate the nonionic polymkeric substance that is made up of following hydrophobic monomer, said hydrophobic monomer is more than one the material of selecting in multipolymer and (methyl) alkyl acrylate and the vinylbenzene of the hydrophobic monomer from (methyl) alkyl acrylate and vinylbenzene, selected and (methyl) propenoate with vinylbenzene property group.

Said polymkeric substance can use separately or mix more than 2 kinds and use.

Shape, the form of polymer beads have no particular limits, can be according to composite silicon dioxide particulate application target, change the particulate size, and form sphere, avette etc.Through changing the size or the size distribution of polymer beads, can suitably modulate the particle diameter of hollow silica particle (A) or the size of hollow bulb.

(hydrophobic organic compound (a-2))

In the present invention, hydrophobic organic compound (a-2) is meant that solvability to water is low, form the compound that is separated with water.Preferably can the dispersive compound in the presence of said quaternary ammonium salt.As such hydrophobic compound, can lift the LogP value is more than 1, is preferably 2～25 compound.

As hydrophobic organic compound (a-2), for example can lift hydrocarbon compound, ester cpds, carbonatoms and be 6～22 lipid acid, carbonatoms and be 6～22 alcohol and silicone wet goods finish; And various base materials such as spices, agricultural chemicals, medicine etc.

Under the situation of using hydrophobic organic compound (a-2); Because the particle diameter of hollow silica particle (A) or the size of hollow bulb can influence the size of the drop of this hydrophobic organic compound, so can wait suitably and adjust through fusing point, temperature of reaction, stirring velocity, the employed tensio-active agent of this hydrophobic organic compound.

(quaternary ammonium salt (b))

Quaternary ammonium salt (b) can be used to the be situated between formation of micropore and the dispersion of polymer beads (a-1) or hydrophobic organic compound (a-2).

R in said general formula (1) and (2) ¹And R ²For carbonatoms is 4～22, preferred carbonatoms is 6～18, be more preferably carbonatoms is 8～16 the straight chain shape or the alkyl of branched.As carbonatoms is 4～22 alkyl, can lift various butyl, various amyl group, various hexyl, various heptyl, various octyl group, various nonyl, various decyl, various dodecyl, various tetradecyl, various hexadecyl, various octadecyl, various eicosyls etc.

X in general formula (1) and (2) is from obtaining the viewpoint of high crystalline, the ion of preferably from 1 valency negatively charged ion such as halide-ions, hydroxide ion, nitrate ion, sulfate ion, selecting more than a kind.As X, preferred halide-ions is more preferably cl ions or bromide anion.

As the represented alkyl trimethyl ammonium salt of general formula (1), can enumerate butyl trimethyl ammonium chloride, hexyl trimethyl ammonium chloride, octyl group trimethyl ammonium chloride, decyl trimethyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, hard ester acyl group trimethyl ammonium chloride, butyl trimethylammonium bromide, hexyl trimethylammonium bromide, octyl group trimethylammonium bromide, decyl trimethylammonium bromide, Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, hard ester acyl group trimethylammonium bromide etc.

As the represented dialkyl dimethyl ammonium salt of general formula (2), can enumerate dibutyl alkyl dimethyl ammonium chloride, dihexyl alkyl dimethyl ammonium chloride, Quaternium 24, dihexyl dimethyl-brometo de amonio, dioctyl dimethyl-brometo de amonio, didodecyldimethylammbromide bromide, two tetradecyl dimethyl-brometo de amonios etc.

In these quaternary ammonium salts (b); Viewpoint from Jie's micropore of formation rule; The alkyl trimethyl ammonium salt of special preferred formula (1) expression; Be more preferably alkyl trimethyl ammonium bromide or alkyl trimethyl ammonium chloride, preferred especially Trimethyllaurylammonium bromide or DTAC.

(silica source (c))

Silica source (c) is through the material of generation silicon alcohol compounds such as hydrolyzable alkoxy TMOS, can lift formula (3)～(7) represented compound.

SiY ₄ (3)

R ³SiY ₃ (4)

R ³ ₂SiY ₂ (5)

R ³ ₃SiY (6)

Y ₃Si-R ⁴-SiY ₃(7)

(in the formula, R ³Separately independently, be illustrated in the organic group of direct combined carbon atom on the Siliciumatom, R ⁴Expression has the alkyl or the phenylene of 1～4 carbon atom, and Y representes to obtain through hydrolysis the monovalence hydrolization group of hydroxyl.)

Further be preferably: in general formula (3)～(7), R ³Independent respectively; The carbonatoms that can be replaced into fluorine atom for the part of Wasserstoffatoms is 1～22 alkyl; Particularly; For carbonatoms is 1～22, preferably carbonatoms is 4～18, further preferably carbonatoms is 6～18, especially preferably carbonatoms is 8～16 alkyl, phenyl or benzyl, R ⁴For carbonatoms 1～4 alkane 2 basis (methylene radical, ethylidene, trimethylene, propane-1; 2-two bases, tetramethylene etc.) or phenylene; Y is that carbonatoms is 1～22, further preferably carbonatoms is 1～8, especially preferably carbonatoms is 1～4 alkoxyl group, perhaps the halogen radical beyond the defluorination.

As the suitable example of silica source (c), can enumerate following compound.

Silane compound, it is in general formula (3), and Y is that carbonatoms is 1～3 alkoxyl group, perhaps the material of the halogen radical beyond the defluorination.

Trialkoxy silane or dialkoxy silicane, they are in general formula (4) or (5), and Y is that carbonatoms is 1～3 alkoxyl group or defluorination halogen radical in addition, R ³For phenyl, benzyl, or a part of Wasserstoffatoms by the substituted carbonatoms of fluorine atom be 1～20, preferred carbonatoms is 1～10, be more preferably carbonatoms is 1～5 alkyl.

Monoalkoxy silane, it is in general formula (6), and Y is that carbonatoms is 1～3 alkoxyl group or defluorination halogen radical in addition, R ³For phenyl, benzyl, or a part of Wasserstoffatoms by the substituted carbonatoms of fluorine atom be 1～20, preferred carbonatoms is 1～10, be more preferably carbonatoms is 1～5 alkyl.

In general formula (7), Y is a methoxyl group, R ⁴Compound for methylene radical, ethylidene or phenylene.

Wherein, preferred especially tetramethoxy-silicane, tetraethoxysilane, phenyl triethoxysilane, 1,1,1-trifluoro propyl triethoxyl silane.

Polymer beads in the aqueous solution of operation A (a-1) or hydrophobic organic compound (a-2) (below, also general name both be " (a) composition "), content such as the following stated of quaternary ammonium salt (b) and silica source (c).

(a-1) content of composition is preferably 0.1～50g/L, further is preferably 0.3～40g/L, is preferably 0.5～30g/L especially.

(a-2) content of composition is 0.1～100mmol/L, and more preferably 1～100mmol/L is preferably 5～80mmol/L especially.

(b) content of composition is preferably 0.1～100mmol/L, is more preferably 1～100mmol/L, is preferably 5～80mmol/L especially, and (c) content of composition is preferably 0.1～100mmol/L, is more preferably 1～100mmol/L, is preferably 5～80mmol/L especially.

The order that contains (a)～(c) composition has no particular limits.For example, can adopt (i) when stirring the aqueous solution, drop into suspension liquid, (b) composition, (c) composition of (a) composition in order; (ii) when stirring the aqueous solution, drop into suspension liquid, (b) composition, (c) composition of (a) composition simultaneously; (iii) drop into suspension liquid, (b) composition, (c) composition of (a) composition, method such as stir then, wherein, preferred (i) method.

In the aqueous solution that contains (a)～(c) composition; As long as do not hinder primary nuclei shell particulate to form; As other composition, can add other compositions such as organic cpds such as methyl alcohol or mineral compound, as noted earlier; If hope to support under the situation of other element beyond silicon-dioxide or the organic group, also can be in manufacturing contains the raw metals such as alkoxyl group salt or halide salt of these metals or after interpolation.

[process B]

Process B is the operation of the aqueous dispersions of modulation primary nuclei shell mould silica dioxide granule.With the aqueous solution that obtains in the operation (A) at 10～100 ℃; Be preferably and stir after the specified time under 10～80 ℃ the temperature; Through leaving standstill; Can on the surface of polymer beads (a-1) or hydrophobic organic compound (a-2), be formed with Jie's micropore, and can separate out the primary nuclei shell mould silica dioxide granule that contains polymer beads (a-1) or hydrophobic organic compound (a-2) in inner packet by quaternary ammonium salt (b) and silica source (c).Though the time of stir process is different with temperature, can form primary nuclei shell mould silica dioxide granule in 0.1～24 hour 10～80 ℃ of following stir process usually.Jie's micropore of the primary nuclei shell mould silica dioxide granule that obtains this moment in addition, is under the state that is filled with tensio-active agent used when making.

Resulting primary nuclei shell mould silica dioxide granule is in water, to obtain under the outstanding turbid state.Can directly use according to purposes, but preferably primary nuclei shell mould silica dioxide granule after separating used.As separation method, can adopt filtration method, centrifugal separation etc.

Contain in the primary nuclei shell mould silica dioxide granule that in operation (B), obtains in the cats product etc., through contacting with acidic solution 1 time or coming decationize tensio-active agent etc. for several times.As used acidic solution, can lift mineral acids such as hydrochloric acid, nitric acid, sulfuric acid; Organic acid such as acetic acid, Hydrocerol A; Zeo-karb etc. is joined the liquid that forms in water or the ethanol etc., still, preferred especially hydrochloric acid.PH can be adjusted to 1.5～5.0 usually.

Through aforesaid method has been removed tensio-active agent from micropore particle, be to have Jie's microvoid structure on the surface, the BET specific surface area is high, and includes the primary nuclei shell mould silica dioxide granule of polymer beads (a-1) or hydrophobic organic compound (a-2).

[operation C, D]

Operation C is the operation of isolated nuclei shell mould silica dioxide granule (B) in the aqueous dispersions that from process B, obtains, and step D is the core-shell silica particle (B) that obtains among the firing process C, thereby obtains the operation of hollow silica particle (A).

In operation C, isolated nuclei shell mould silica dioxide granule (B) from aqueous dispersions according to necessity, can contact with acidic aqueous solution, washes, drying.In addition, after at high temperature handling, in the step D, in electric furnace etc.,, remove inner superpolymer (a-1) or hydrophobic organic compound (a-2) preferably under 350～800 ℃, further preferably under 450～700 ℃, burning till 1～10 hour.The basic comprising of the housing department of the hollow silica particle (A) that obtains does not change, but inner high molecular polymer (a-1) or hydrophobic organic compound (a-2) are removed through burning till.

In the present invention; Owing to burn till the core-shell silica particle that includes polymkeric substance (a-1) or hydrophobic organic compound (a-2); Therefore be desirable state particularly, so can easily make hollow silica particle (A) with institute's desirable shape, form through shape, the form of controlling entrapped polymer beads (a-1) in advance.For example, through burning till the core-shell silica particle that inside has the spheric polymkeric substance, can make inner hollow and profile is spheric hollow silica particle (A).

In the above-mentioned hollow silica particle (A) and core-shell silica particle (B) that obtains, preferably in powder x-ray diffraction is measured, with interplanar distance (d) be the particle at demonstration peak under the diffraction angle that 1nm～the 12nm scope is suitable (2 θ).

The average micropore diameter of Jie's microvoid structure of the hollow silica particle (A) that in operation (I), obtains is preferably 1～8nm; Be more preferably 1～5nm, hope that 70 quality % of hollow silica particle (A) are above, be preferably more than the 75 quality %, further be preferably above this Jie's micropore diameter that is had of 80 quality % in average micropore diameter ± 30 quality %.

In addition, the BET specific surface area of hollow silica particle (A) is preferably 100～1500m ²/ g further is preferably 200～1500m ²/ g is more preferably 300～1500m ²/ g.

The median size of hollow silica particle (A) is preferably 0.05～4 μ m, further is preferably 0.05～3.5 μ m, is more preferably 0.1～3.0 μ m.

The mean thickness of housing department (mesoporous silicon oxide portion) be preferably can keep with the hollow silica particle as the scope of the intensity of carrier in thin thickness; From maintaining the viewpoint of more encapsulation object, the mean diameter (average volume) of preferred hollow bulb is bigger.From such viewpoint, the mean thickness of housing department is generally 0.5～500nm, is preferably 2～400nm, is more preferably 3～300nm.

In addition, the ratio of [mean thickness of housing department/hollow silica particulate median size] is generally 0.01～0.9, is preferably 0.05～0.8, is more preferably 0.1～0.7.

The mensuration of the median size of hollow silica particle (A), average outer casing thickness, BET specific surface area, average micropore diameter and powder x-ray diffraction (XRD) pattern can be carried out according to the method for embodiment record.

Operation (II)

Operation (II) is that hollow silica particle (A) that obtains in the operation (I) or core-shell particle (B) are being burnt till above under 950 ℃ the temperature, with the operation of modulation hollow silica particle (C).

Sintered microporous from suitably, making median size is 0.05～3 μ m, and the BET specific surface area is less than 30m ²The viewpoint of/g is set out, and firing temperature is preferably 960～1500 ℃, is more preferably 970～1300 ℃, further is preferably 980～1200 ℃.

Burn till and can use electric furnace etc. to carry out, firing time is according to the difference of firing temperature and difference, but is generally 0.5～100 hour, is preferably 1～80 hour.

In the present invention; In case in operation (I), made hollow silica particle (A); Through in operation (II), it being burnt till above under 950 ℃ the temperature; Can not change the substruction of the hollow silica particle (A) of gained in the operation (I), and obtain the hollow silica particle (C) that median size and BET specific surface area reduce.In addition, also can the core-shell silica particle (B) that obtain in the operation (I) directly burnt till above under 950 ℃ the temperature, thereby obtain hollow silica particle (C).In the present invention, made hollow silica particle (A), further burnt till then and obtain the method for the hollow silica particle (C) that the BET specific surface area reduces in case be more preferably.

Operation (III)

Operation (III) is the hollow silica particle (C) that obtains in the operation (II) to be scattered in matrix resin form the operation of modulating dispersion liquid in the material.

(matrix resin)

The matrix resin that can use among the present invention has no particular limits.For example, can lift through heating the hardened thermosetting resin, through rayed such as ultraviolet rays and hardened light hard resin, and thermoplastic resin.

As thermosetting resin and light hard resin, can enumerate epoxy resin, unsaturated polyester resin, resol, urea-melmac, urethane resin, silicone resin, diallyl phthalate resin etc.

As epoxy resin, can lift various epoxy resin such as glycidyl ether type, glycidyl ester type, glycidic amine type, annular aliphatic type, lacquer resins (novolak) type, naphthalene type, dicyclopentadiene type such as bisphenol A type epoxy resin.

As unsaturated polyester resin, can lift phthalic acid system, m-phthalic acid system, terephthalic acid system, ester ring type unsaturated acid system, fatty formula saturated acid system, bis-phenol system, contain the various unsaturated polyester resins of hydracid system, Halogen bis-phenol system.

As resol, can lift the resol of resole type, lacquer resins type etc.

As thermoplastic resin, can lift polyolefin resin, PVC RESINS, vinylidene chloride resin, polystyrene resin, acrylonitrile butadient styrene resin, acrylonitrile styrene copolymer resin, styrene block copolymer resin, methacrylic resin, polyvinyl alcohol resin, polyamide resin, polyacetal resin, polycarbonate resin, modified polyphenylene ether resin, thermoplastic polyester, fluoro-resin, polyphenylene sulfide, polysulfone resin, non-crystalline state aromatic ester resin, polyetherimide resin, polyethersulfone resin, polyether ketone resin, liquid crystal polymer resin, polyamide-imide resin, thermoplastic polyimide resin, a rule (syndio) is a polystyrene resin etc.

As polyolefin resin, can enumerate polyvinyl resin, acrylic resin, alpha-olefin copolymer resin, polybutene-1 resin, polymethylpentene resin, cycloolefin fluoropolymer resin, ethylene vinyl acetate resin, ethylene methacrylic acid copolymer resin, ionomer etc.

As polyamide resin, can enumerate nylon 6, nylon 66, Ni Long11, nylon 12 etc.

As thermoplastic polyester, can lift pet resin, polybutylene terephthalate resin, poly butylene succinate resin, polylactic resin etc.

As fluorine resin, can lift teflon resin, PFA resin, fluorinated ethylene propylene copolymer resin, ethylene tetrafluoroethylene copolymer resin, polyvinylidene fluoride resin, daiflon, ethene chlorotrifluoroethylene resin, tetrafluoroethylene perfluor dioxole copolymer resin, polyfluoroethylene resin etc.

In said matrix resin, preferred thermosetting resin and light hard resin from the low electrochemical viewpoint that is situated between, are more preferably epoxy resin, resol, special preferred epoxy.Matrix resin can use separately and a kind ofly also can mix use more than 2 kinds.

The weight-average molecular weight of matrix resin is preferably 200～100, and 000, be more preferably 500～10,000.

From the viewpoint of performance of performance low dielectric film, the content of matrix resin is preferably 30～98 quality %, is more preferably 40～95 quality %, further is preferably 50～95 quality %, more further is preferably 60～90 quality %.

[method of manufacture and the low dielectric film of low dielectric film are used the coating agent]

The method of manufacture of low dielectric film of the present invention is characterised in that: comprise aforementioned operation (I)～(III) and following operation (IV).

In addition, " matrix resin formation material " is meant the material that has flowability, is solidified to form matrix resin under certain condition.For example comprise: thermosetting resin or light hard resin are dissolved in material, the material of thermoplastic resin before polymerization or the material in polymerization process that forms in the volatile solvent at resin material, the thermoplastic resin material of presclerotic liquid state through becoming material, thermoplastic resin material with mobile state after heating.

Low dielectric film of the present invention is under the situation of thermosetting resin or light hard resin at matrix resin; Be to form material as matrix resin through resin material with presclerotic liquid state; To disperse, hollow silica dioxide granule (C) wherein, make matrix resin form hardened material then and the solidified method obtains.

In addition; At matrix resin is under the situation of thermoplastic resin, can form in the material disperse, hollow silica dioxide granule (C) at the matrix resin of the fluidization through heating through (1); Cooling forms in the material its solidified method, (2) matrix resin in being dissolved in volatile solvent then; Disperse, hollow silica dioxide granule (C) makes solvent evaporates then and its solidified method, (3) is formed in the material at the matrix resin as monomer or intermediate polymer, disperse, hollow silica dioxide granule (C); Begin polymerization then and make its solidified method, (4) in being in polymerization and in the formation of the matrix resin before the solidifying material; Disperse, hollow silica dioxide granule (C) makes the polymerization completion and solidified method etc. obtain low dielectric film of the present invention.

The 1st low dielectric film of the present invention is used the coating agent, it is characterized in that, is formed in the material in matrix resin by the hollow silica particles dispersed and forms, and said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m ²/ g.

The 2nd low dielectric film of the present invention is used the coating agent; It is characterized in that; Form in the material in matrix resin by the hollow silica particles dispersed and form; Said hollow silica particulate median size is 0.05～1 μ m, all have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.

The 3rd low dielectric film of the present invention is used the coating agent; It is characterized in that formed in the material in matrix resin by the hollow silica particles dispersed and form, said hollow silica particulate median size is 0.05～3 μ m's; Porosity is 30～90%, and the BET specific surface area is less than 30m ²/ g.

These low dielectric films are disperse, hollow silica dioxide granules in having mobile matrix resin formation material with the coating agent; With it in said operation (IV); Be coated on the substrate as the dispersion liquid in the operation (III), make its curing then, form low dielectric film thus.

Used substrate has no particular limits, and can lift silicon chip, Si ₃N ₄, metal sheet (Al, Pt etc.), sheet glass etc., also comprise substrates as thin as a wafer such as tinsel.

The coating of coating agent (dispersion liquid) can be carried out through domestic methods such as spin-coating method, dip coating, spread coating, spraying method, intaglio plate coating methods.

Curing after the coating coating agent can be through dry and even heating, and perhaps rayed is carried out.

Dry and even heating is according to the purposes of the composition of membrane structure or material, film and difference; But viewpoint from productivity, the easy property of production; Can be preferably in room temperature～300 ℃, further be preferably 50～200 ℃, further be preferably under 70～150 ℃ the temperature; The preferred maintenance 0.5～20 day, be more preferably maintenance and carry out over 1～10 day.

From the performance of performance low dielectric film and the viewpoint of disperseing easy property, the viscosity of preferred substrate resin formation material is 0.1～20Pas, further is preferably 0.2～18Pas, is more preferably 1～16Pas, is preferably 2～15Pas especially.In addition, the mensuration of viscosity can be carried out according to the method that embodiment put down in writing.

Matrix resin forms material and hollow silica particulate mixing time and needs only and can make this silica dioxide granule equably in the dispersive scope from seeing in appearance; Be preferably the short period of time; Be preferably 0.1～60 minute, be more preferably 0.5～10 minute, be more preferably 0.5～2 minute.In addition, preferably both are being mixed and after the modulation dispersion liquid, coating as early as possible and solidify on the substrate, beginning to be preferably 0.1～60 minute, be more preferably 0.1～10 minute, be more preferably 0.1～2 minute to the time of coating from the modulation dispersion liquid.In addition, both uniform mixing can stir through scraper (Spatula), magnetic stirs, blade (blade) stirs, clarifixator domestic methods such as (homo mixer) is carried out.

Perhaps bring into play the viewpoint of the performance of resulting low dielectric film from being coated with operability, the hollow silica particulate content that is contained in the coating agent is preferably 10～70 quality %, is more preferably 15～50 quality %.In the coating agent, also can contain solvent (dispersion solvent), according to the kind of resin etc., alcohols solvent usually.

Low dielectric film of the present invention is with coating agent and low dielectric film; With the hollow silica particle; In the scope that does not hinder the object of the invention, can contain mesoporous silica particles, still with hollow structure; From the low electrochemical viewpoint that is situated between, preferably do not contain mesoporous silica particles with hollow structure.

In addition, low dielectric film of the present invention and coating agent can contain known inhibitor, photostabilizer, static inhibitor, nucleophilic reagent, fire retardant, softening agent, stablizer, tinting material (pigment, dyestuff), antiseptic-germicide, tensio-active agent, coupling agent, releasing agent etc.

Embodiment

In following manufacturing example, embodiment and comparative example, " % " expression " quality % ".

Make the hollow silica particle that obtains in the example, and the various mensuration of the low dielectric film that obtains among the embodiment, comparative example are carried out through following method.

(1) hollow silica particulate powder x-ray diffraction (XRD) is measured

Use the powder x-ray diffraction device (Liue electrical machinery Industrial Co., Ltd makes, trade(brand)name: RINT 2500VPC), at x-ray source: Cu-k α; Tube voltage: 40mA; Tube current: 40kV, the SI (Sampling pitch): 0.02 °, divergent slit (Divergence slit): 1/2 °; Divergent slit fore-and-aft distance 1.2mm, scatter slit (Scatter slit): 1/2 ° and reception slit (Receiving slit): carry out powder x-ray diffraction under the condition of 0.15mm and measure.Use continuous sweep method, with sweep limit be set at 1～20 ° of diffraction angle (2 θ), sweep velocity is set at 4.0 °/minute.In addition, mensuration is chippy test portion to be loaded on aluminium sheet carry out.

(2) observation of hollow silica particulate particle shape

Use high resolution field emission scanning electron microscope (Hitachi Co., Ltd's manufactured, trade(brand)name: FE-SEM S-4000) carry out the observation of particle shape.

(3) measure hollow silica particulate average primary particle diameter, average hollow bulb diameter and average housing department thickness

(Jeol Ltd. makes, trade(brand)name: JEM-2100) under acceleration voltage 160kV, carry out particulate and observe to use transmission electron microscope (TEM).Actual measurement includes whole particulate diameters, hollow bulb diameter and the housing department thickness in 5 visuals field of 20～30 particulate on photo, obtains average primary particle diameter, average hollow bulb diameter and average housing department thickness.Further, through calculating obtain particle diameter be median size ± 30% with interior particle with respect to whole proportion of particles (quality %).In addition, observe to be to use sample is attached to and have on the copper mesh (thing of should consulting and deliberating Co., Ltd. makes, the 200-A net) of high resolution with the carbon supporting film, and the sample that unnecessary sample blowing is processed carries out.

(4) mensuration of hollow silica particulate BET specific surface area and average micropore diameter

Use specific surface area micropore measure of spread device (Shimadzu Corporation makes, trade(brand)name: ASAP 2020), measure the BET specific surface area through the multipoint method that adopts liquid nitrogen, derived parameter C is the positive interior value of scope.The BJH method is adopted in the derivation of BET specific surface area, with its summit value as average micropore diameter.Under 250 ℃, sample carried out 5 hours pre-treatment.

(5) mensuration of dielectric constant, tangent of the dielectric loss angle

The mixing miscellany that hollow silica particle and resin are arranged of coating after the heat hardening, is peeled off resin combination from film on the PET film, is cut into the bar-shaped sample that obtains.Perhaps; The ditch that on TEFLON (registered trademark) resin, digs out width and be 2mm, the degree of depth and be 1.5mm, length and be 120mm injects the mixing miscellany that hollow silica particle and resin are arranged to make mold in this mold, make its heat hardening; After the cooling, from mold, take out sample.No matter the electric property of the sample of which kind of method gained is all the same.

Use is at the PNA of Agilent manufactured microwave network analyzer " E8361A " (10MHz～67GHz) go up connection Co., Ltd. Northeast electronic application to develop the specific inductivity determinator (syntonizer of making; 5.8GHz) device that forms; Use based on resonant cavity perturbation method; Under the frequency of 1MHz or 5.8GHz, measure the specific inductivity and the tangent of the dielectric loss angle of sample in early stage.

At specific inductivity is below 3.5, and tangent of the dielectric loss angle is under the situation below 0.01, is the low dielectric film with sufficient insulating property.

(6) hollow silica particulate measurement method of porosity

Porosity (%) is to use the ULTRAPYCNOMETER1000 of QUANTACHROME manufactured, through the density of measuring as mensuration gas with helium and nitrogen, calculates according to following formula.

Porosity (%)=(utilize the mensuration density of nitrogen/utilize the mensuration density of helium) * 100

(7) volume ratio of resin combination air calculates

The volume ratio of resin combination air (%) is through the combination ratio of resin combination and the density of resin and silicon-dioxide, and through the hollow silica particulate porosity that try to achieve said (6), calculates according to following formula.The density of resin is respectively: epoxy resin: 1.1g/cm ³, polyimide resin: 1.48g/cm ³, silicon dioxide skeleton: 2.2g/cm ³

The density of the mass ratio * resin of the volume=resin of resin

The density of the mass ratio * silicon-dioxide of the volume=silicon-dioxide of silicon-dioxide shell

Volume * the porosity of the volume of air=silicon-dioxide shell/(1-porosity)

The volume of the volume ratio of the air in the resin combination (%)=air/(volume of the volume+air of the volume of resin+silicon-dioxide shell)

Make example 1 (manufacturing of hollow silica particle (1))

In the reactive tank of 20L; 25% TMAH, 68g Trimethyllaurylammonium bromide and the 192g cationic acrylic polymer particle (Japanese Paint Co., Ltd. make trade(brand)name: FINE SPHERE FS-501, median size 500nm) that add 16kg water, 66g stir; In this aqueous solution; Slowly add the 68g tetramethoxy-silicane, after room temperature (25 ℃) stirs 5 hours down, make its slaking 12 hours.

Next; It is after the membrane filter of 0.2 μ m filters that the white depositions that obtains is used the aperture; Clean with 10L water, drying is 5 hours under 100 ℃ temperature condition, and obtaining with the polymer beads is that nuclear, silica dioxide granule are the core-shell silica particulate dried powder of shell.

The dried powder of gained is used the electric furnace that heats up at a high speed (MOTOYAMA Co., Ltd. manufacturing; Trade(brand)name: SK-2535E); Through when feeding air-flow (3L/min), its speed with 1 ℃/minute being warming up to 600 ℃; And under 600 ℃, burn till and removed organic composition in 2 hours, obtain hollow form silica dioxide granule (1).This hollow form silica dioxide granule of 50g is moved in the jar of aluminum, use said electric furnace, under air, burnt till 72 hours with 1000 ℃.

Mensuration result such as the following stated of hollow form silica dioxide granule after burning till.

Average primary particle diameter is 480nm, and average hollow bulb diameter is 400nm, and average housing department thickness is 40nm, and the BET specific surface area is 15m ²/ g.

All particulate 99.9 quality % have median size ± 30% with interior particle diameter.

Through the mensuration of average micropore diameter, confirm more than 1nm, not have the peak.

In powder x-ray diffraction is measured, confirm locating there is not the peak less than the suitable diffraction angle of the scope of 1nm (2 θ) with spacing (d).

Make example 2 (manufacturings of hollow silica particle (2))

In the reactive tank of 20L, adding 4kg methyl alcohol, 25% TMAH of 33g, 68g Trimethyllaurylammonium bromide, 40g hexane stir, and dissolving.In this methanol solution, in 70 seconds, add the 12kg ion exchanged water, separate out the emulsion droplet of hexane.120 seconds of stirred solution slowly add the 68g tetramethoxy-silicane afterwards, after room temperature (25 ℃) stirs 5 hours down, make its slaking 12 hours.

Next, the white depositions that the filter paper (5C) that uses ADVANTEC to make filters gained, with the water cleaning of 10L, drying is 5 hours under 100 ℃ temperature condition, obtains the dried powder of silica dioxide granule.

The dried powder of gained is used the electric furnace that heats up at a high speed (OTOYAMA Co., Ltd. of M Co., Ltd. manufacturing; Trade(brand)name: SK-2535E); Through when feeding air-flow (3L/min), its speed with 1 ℃/minute being warming up to 600 ℃; And under 600 ℃, burn till and removed organic composition in 2 hours, obtain hollow silica particle (2).This hollow silica particle of 50g is moved in the jar of aluminum, use said electric furnace, under air, burnt till 72 hours with 1000 ℃.

Mensuration result such as the following stated of hollow silica particle 1 after burning till.

Average primary particle diameter is 847nm, and average hollow bulb diameter is 615nm, and average housing department thickness is 116nm, and the BET specific surface area is 8m ²/ g, porosity is 40%.

All particulate 90 quality % have median size ± 30% with interior particle diameter.

In powder x-ray diffraction is measured, confirm locating there is not the peak at a distance from (d) less than the suitable diffraction angle of the scope of 1nm (2 θ) with interplanar.

Make example 3 (manufacturings of hollow silica particle (3))

Except the interpolation time with ion exchanged water is decided to be 300 seconds, the churning time till the interpolation tetramethoxy-silicane was decided to be outside 300 seconds, and other all obtains hollow silica particle (3) with manufacturing example 2 equally.

Hollow silica particulate after burning till is measured the result and is described below.

Average primary particle diameter is 1317nm, and average hollow bulb diameter is 955nm, and average housing department thickness is 181nm, and the BET specific surface area is 4m ²/ g, porosity is 40%.

Embodiment 1

It is mixing with the 1.4g matrix resin 0.6g to be made the hollow silica particle (1) that obtains in the example 1, makes low dielectric resin composition, wherein; Said matrix resin is that (Japan Epoxy Resins Co.Ltd. makes with bisphenol A type epoxy resin; Liquid-type, grade: 828 (2～3 aggressiveness), viscosity: 12～15Pas (25 ℃); 184～194), (Japan Epoxy Resins Co.Ltd. makes epoxy resin hardener epoxy equivalent (weight):; Acid anhydrides grade: YH306), (Japan Epoxy Resins Co.Ltd. makes hardening accelerator, 2-ethyl-4 (5)-Methylimidazole, grade: EM124) mix with 5: 6: 0.05 weight ratio and obtain.This compsn is injected the mold that said TEFLON (registered trademark) makes, in electric drying apparatus,, further made it sclerosis in 6 hours, after the cooling, from mold, take out sample with 120 ℃ of heating with after 80 ℃ of heating 3 hours.Use this sample determination specific inductivity, tangent of the dielectric loss angle.Its result is as shown in table 1.

Embodiment 2

Except in embodiment 1, the hollow silica particle being become 0.8g, matrix resin becomes outside the 1.2g, and other all makes low dielectric resin composition with embodiment 1 equally, and makes sample.

Comparative example 1

Except in embodiment 1, not using the hollow silica particle, other all makes low dielectric resin composition with embodiment 1 equally, and makes sample.

Comparative example 2

Except in embodiment 1, using hollow silica particle (the specific surface area 1200m that in making example 1, only under 600 ℃, burnt till 2 hours and obtain ²/ g) outside and the same low dielectric resin composition of making of embodiment 1, and make sample.

Embodiment 3

It is mixing that 0.6g is made the hollow silica particle and the 7g polyimide resin (Ube Industries, Ltd makes, trade(brand)name U-Varnish S (solid state component 20%)) that obtain in the example 1, makes low dielectric resin composition.This compsn is injected the mold that said TEFLON (registered trademark) makes, in electric drying apparatus, took out sample in 10 minutes afterwards, further in firing furnace, heated 10 minutes down, and make sample at 450 ℃ with 200 ℃ of heating.Use this sample determination specific inductivity, tangent of the dielectric loss angle.Its result is as shown in table 1.

Comparative example 3

Except in embodiment 3, not using the hollow silica particle, other all makes low dielectric resin compositions with embodiment 3 equally, and the perparation of specimen.

[table 1]

^*1: under 600 ℃, burn till, specific surface area is 1200m ²/ g

Can know from table 1; Contain and contain the low dielectric resin composition of epoxy resin as matrix resin in hollow silica particulate embodiment 1 and 2, its specific inductivity is respectively 2.31 and 2.29, and tangent of the dielectric loss angle is respectively 0.0078 and 0.0068; And by comparison; Do not contain the resin combination in the hollow silica particulate comparative example 1, its specific inductivity height to 2.65, tangent of the dielectric loss angle height to 0.0112.And then, contain the specific surface area height to 1200m ²The comparative example 2 of the hollow particle of/g, its specific inductivity height to 2.63, tangent of the dielectric loss angle height to 0.0129.In addition; Contain the low dielectric resin composition of polyimide resin as matrix resin among the embodiment 3, its specific inductivity is 2.99, and tangent of the dielectric loss angle is 0.0015; And by comparison; Do not contain the resin combination in the hollow silica particulate comparative example 3, its specific inductivity height to 3.7, tangent of the dielectric loss angle height to 0.0017.

Hence one can see that; The hollow silica particulate low dielectric resin composition that contains involved in the present invention; Compare with the resin combination that does not contain hollow silica particulate comparative example 1 or 3; Perhaps higher with containing specific surface area hollow silica particulate comparative example 2 is compared, and in practicality, obviously has significant low-k, low-dielectric loss angle tangent.

Embodiment 4

It is mixing with the 1.4g matrix resin 0.6g to be made the hollow silica particle (2) that obtains in the example 2; Make low dielectric resin composition, said matrix resin is that (Japan Epoxy Resins Co.Ltd. makes, liquid-type with bisphenol A type epoxy resin; Grade: 828 (2～3 aggressiveness); Viscosity: 12～15Pas (25 ℃), 184～194), (Japan Epoxy Resins Co.Ltd. makes epoxy resin hardener, the acid anhydrides grade: YH306), (Japan Epoxy Resins Co.Ltd. makes hardening accelerator epoxy equivalent (weight):; 2-ethyl-4 (5)-Methylimidazole, grade: EM124) mix with 5: 6: 0.05 weight ratio and obtain.This compsn is injected the mold that said TEFLON (registered trademark) makes, in electric drying apparatus,, further made it sclerosis in 6 hours, after the cooling, from mold, take out sample with 120 ℃ of heating with after 80 ℃ of heating 3 hours.Use this sample determination specific inductivity, tangent of the dielectric loss angle.Its result is as shown in table 2.

Embodiment 5

The hollow silica particle (3) that in embodiment 4, using manufacturing example 3, obtains replaces making the hollow silica particle (2) that obtains in the example 2, and other all makes low dielectric resin compositions with embodiment 4 equally, and the making sample.

Comparative example 4

Make the hollow silica particle (2) that obtains in the example 2 except in embodiment 4, not using, other all makes low dielectric resin compositions with embodiment 4 equally, and makes sample.

[table 2]

	Embodiment 4	Embodiment 5	Comparative example 4
				Resin	Epoxy resin	Epoxy resin	Epoxy resin
Hollow silica particulate content (%)	30	30
				Specific inductivity (5.8GHz)	2.42	2.42	2.65
Tangent of the dielectric loss angle	0.0086	0.0082	0.0112

Can know from table 2; Contain and contain the low dielectric resin composition of epoxy resin as matrix resin in hollow silica particulate embodiment 4 and 5, its specific inductivity is 2.42, and tangent of the dielectric loss angle is respectively 0.0086 and 0.0082; And by comparison; Do not contain the resin combination in the hollow silica particulate comparative example 4, its specific inductivity height to 2.65, tangent of the dielectric loss angle height to 0.0112.

Hence one can see that, and the hollow silica particulate low dielectric resin composition that contains involved in the present invention is compared with not containing hollow silica particulate comparative example 4, in practicality, obviously has significant low-k, low-dielectric loss angle tangent.

Utilize possibility on the industry

According to the present invention, the method for manufacture and the low dielectric film of low dielectric film, low dielectric resin composition and the low dielectric film that low dielectric resin composition with enough low specific inductivity, tangent of the dielectric loss angle can be provided, is formed by this low dielectric resin composition are used the coating agent.

Claims

1. low dielectric resin composition, wherein,

Said low dielectric resin composition by the hollow silica particles dispersed in matrix resin and form,

Said hollow silica particulate median size is 0.05～3 μ m, and the BET specific surface area is less than 30m ²/ g.

2. low dielectric resin composition, wherein,

Said hollow silica particulate median size is 0.05～1 μ m, all have median size ± 30% with interior particle diameter more than the 80 quality % in the particle, and the BET specific surface area is less than 30m ²/ g.

3. low dielectric resin composition, wherein,

Said hollow silica particulate median size is 0.05～3 μ m, and porosity is 30～90%, and the BET specific surface area is less than 30m ²/ g.

4. like each described low dielectric resin composition in the claim 1～3, wherein,

The hollow silica particle is locating do not show peak at a distance from (d) less than the suitable diffraction angle of the scope of 1nm (2 θ) with interplanar in powder x-ray diffraction is measured.

5. like each described low dielectric resin composition of claim 1～4, wherein,

Hollow silica particulate content is 10～60 quality %.

6. like each described low dielectric resin composition in the claim 3～5, wherein,

The volume ratio of resin combination air is 3～60%.

7. low dielectric film, it is formed by each described low dielectric resin composition in the claim 1～6.

8. the method for manufacture of the described low dielectric resin composition of claim 1～7, wherein,

Said method of manufacture comprises following operation (I)～(III):

Operation (I): the hollow silica particle (A) of air is contained in particle modulator inside, perhaps modulates core-shell silica particle (B), and said core-shell silica particle (B) is encapsulated with through burning till to disappear and forms the material of hollow part;

Operation (II): the said hollow silica particle (A) or the said core-shell silica particle (B) that under surpassing 950 ℃ temperature, obtain in operation (I) burn till, with modulation hollow silica particle (C);

Operation (III): the hollow silica particle (C) that obtains in the operation (II) is scattered in matrix resin forms in the material and modulate dispersion liquid.

9. the method for manufacture of a low dielectric film, wherein,

Said method of manufacture comprises aforementioned operation (I)～(III) and following operation (IV):

Operation (IV): the dispersion liquid that obtains in the said operation (III) is coated on the substrate, made its curing then.

10. like the method for manufacture of claim 10 or 11 described low dielectric films, wherein,

The viscosity that matrix resin forms material is 0.1～20Pas.

11. a low dielectric film is used the coating agent, wherein,

Said coating agent is formed in the material in matrix resin by the hollow silica particles dispersed and forms,

12. a low dielectric film is used the coating agent, wherein,

13. a low dielectric film is used the coating agent, wherein,

14. the purposes of each described low dielectric resin composition in low dielectric film in the claim 1～6.